Aminothiazoles

ABSTRACT

Aminothiazoles of the formula ##STR1## or the tautomers thereof, where R 1  and R 2  are each hydrogen or together form a radical of the formula ##STR2## where T 1  is hydrogen, alkyl or phenyl, T 2  and T 3  are each, independently of one another, alkyl or phenyl, or T 2  and T 3  form, together with the nitrogen atom connecting them, a heterocyclic radical, R 3  is substituted mercapto or substituted amino and R 4  is alkanoyl, benzoyl, cyano or ##STR3## where T 4  is hydroxyl, C 1  -C 6  -alkoxy, amino or R 3 , T 5  is hydrogen, alkyl or phenyl and T 6  is the radical of a primary amine or of an active methylene compound, are prepared as described.

This application is a continuation-in-part of application Ser. No. 07/631,430, filed on Dec. 21, 1990, now abandoned.

The present invention relates to novel aminothiazoles of the formula I ##STR4## or the tautomers thereof, where R¹ and R² are each hydrogen or together form a radical of the formula ##STR5## where T¹ is hydrogen, C₁ -C₆ -alkyl or phenyl and T² and T³ are identical or different and each, independently of one another, is C₁ -C₆ -alkyl, C₅ -C₇ -cycloalkyl or phenyl, or T² and T³ form, together with the nitrogen connecting them, a 5- to 7-membered saturated heterocyclic radical which may contain further hetero atoms, R³ is

    --S(O).sub.n --X,

where n is 0, 1 or 2 and X is substituted or unsubstituted C₁ -C₂₀ -alkyl, C₃ -C₈ -cycloalkyl, substituted or unsubstituted C₃ -C₆ -alkenyl, substituted or unsubstituted C₃ -C₆ -alkynyl, substituted or unsubstituted phenyl or, if n is 0, also hydrogen, or R₃ is Y which means mono- or di-C₁ -C₂₀ -alkylamino, where the alkyl may be substituted and/or interrupted by one or more oxygen atoms, C₃ -C₆ -cycloalkylamino, adamantylamino, mono- or di-C₂ -C₁₂ -alkenylamino, C₃ -C₁₂ -alkynylamino, N-(C₁ -C₅ -alkyl)-N-phenylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)-piperazino, hexamethyleneimino, 1-imidazolyl, 1-pyrazolyl, substituted or unsubstituted phenylamino, pyridylamino, thienylamino, hydrazino, mono- or di-C₁ -C₄ -alkylhydrazino or phenylhydrazino and R⁴ is C₁ -C₆ -alkanoyl, benzoyl, cyano or ##STR6## where T⁴ is hydroxyl, C₁ -C₅ -alkoxy, amino or the abovementioned radical Y, T⁵ is hydrogen, C₁ -C₅ -alkyl or phenyl and T⁶ is the radical of an active methylene compound, hydroxyimino or N-Q where Q is C₁ -C₂₀ -alkyl which may be substituted and may be interrupted by one or more oxygen atoms, or C₃ -C₆ -alkenyl, C₃ -C₂₀ -alkynyl, C₃ -C₁₂ -cycloalkyl or phenyl, each of which may be substituted, pyridyl, C₁ -C₄ -alkoxycarbonylmethyl, amino, i-C₁ -C₄ -alkylamino or phenylamino, with the proviso that

a) R³ is not ##STR7## when R¹ and R² are each hydrogen and R⁴ is acetyl or ethoxycarbonyl,

b) R³ is not methylthio when R¹ and R² are each hydrogen and R⁴ is cyano, and

c) R¹ and R² are not both hydrogen when R³ is piperidino or morpholino and R⁴ is cyano.

Tetrahedron Lett. 22 (1982) 2285-2288 has disclosed the compound 2-amino-4-methylthio-5-cyanothiazole. Furthermore, Tetrahedron Lett. 28 (1987) 117-120 describes 2-aminothiazoles which have either acetyl or ethoxycarbonyl in position 5 and ##STR8## in position 4.

2,4-Diaminothiazole derivatives having a substituted amino group in position 2, a piperidino or morpholino group in position 4 and a cyano group in position 5 have also been disclosed (see, for example, Tetrahedron Lett. 22 (1981) 2285-2288).

However, these thiazoles are not especially suitable as diazo components for preparing azo dyes.

It was an object of the present invention to provide novel 2-aminothiazoles which have a mercapto group or a substituted amino group in position 4 and are intended to be especially suitable as diazo component or precursor thereof for preparing azo dyes.

We have accordingly found the aminothiazoles of the formula I defined above.

All the alkyl and alkenyl groups in the abovementioned formula I can be either straight-chain or branched.

Alkyl groups interrupted by one or more oxygen atoms in the formula I are preferably interrupted by from 1 to 3, in particular 1 to 2, oxygen atoms.

Examples of possible substituents for phenyl groups in the formula I are C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen, especially fluorine, chlorine or bromine, nitro, hydroxyl, amino, mono- or di-C₁ -C₆ -alkylamino, acetylamino, carboxyl, carbamoyl, thiocarbamoyl, cyano, C₁ -C₆ -alkoxycarbonyl, trifluoromethyl, hydroxy-C₁ -C₃ -alkyl or C₁ -C₄ -alkanoyl.

Examples of possible substituents for alkyl groups in the formula I are hydroxyl, C₁ -C₆ -alkoxy, phenyl-C₁ -C₄ -alkoxy, phenoxy, amino, mono- or di-C₁ -C₆ -alkylamino, phenyl-C₁ -C₆ -alkylamino, diphenyl-C₁ -C₄ -alkylamino, phenylamino, diphenylamino, mono- or di-C₃ -C₆ -cycloalkylamino, C₃ -C₆ -cycloalkyl, hydroxy-C₁ -C₆ -alkylamino, morpholino, piperazino, N-(C₁ -C₆ -alkyl)piperazino, thiomorpholino, piperidino, pyrrolidino, hexamethyleneimino, 2-thienyl, 2-furyl, 1H-pyrrol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, phenyl, carboxyl, C₁ -C₃ -alkoxycarbonyl, carbamoyl, mono- or di-C₁ -C₄ -alkylcarbamoyl, cyano, thiocarbamoyl, phenoxycarbamoyl, phenyl-C₁ -C₄ -alkoxycarbonyl, mono- or diphenylcarbamoyl, mono- or di(phenyl-C₁ -C₄ -alkyl)carbamoyl, mono- or diphenylthiocarbamoyl, mono- or di(phenyl-C₁ -C₄ -alkyl)thiocarbamoyl, C₁ -C₆ -alkylthio, phenylthio or phenyl-C₁ -C₄ -alkylthio.

Examples of possible substituents for alkenyl, alkynyl or cycloalkyl groups in the formula I are fluorine, chlorine or bromine.

When T² and T³ form, together with the nitrogen connecting them, a 5- to 7-membered saturated heterocyclic radical which may contain further hetero atoms, possible examples are pyrrolidino, piperidino, morpholino, thiomorpholino, thiomorpholino S,S-dioxide, piperazino, N-(C₁ -C₄ -alkyl)piperazino or hexamethyleneimino.

Examples of T¹, T², T³ and T⁵ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl or hexyl.

Examples of R⁴ are formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl or hexanoyl.

(The names isooctyl, isononyl, isodecyl and isotridecyl used hereinafter are trivial names derived from the alcohols obtained by the oxo synthesis (cf. Ullmanns Encyklopadie der technischen Chemie, 4th Edition, Volume 7, pages 215 to 217 and Volume 11, pages 435 and 436.)

The radical --NQ is derived from a primary amine of the formula H₂ NX. Examples are methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, neopentylamine, hexylamine, heptylamine, n-octylamine, isooctylamine, 2-ethylhexylamine, nonylamine, isononylamine, decylamine, isodecylamine, undecylamine, dodecylamine, tridecylamine, isotridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, allylamine, methallylamine, propargylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclononylamine, cyclodecylamine, cycloundecylamine, cyclododecylamine, 2-hydroxyethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-hydroxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-(2-phenoxyethoxy)propylamine, 3-benzyloxypropylamine, 2-(N,N-dimethylamino)ethylamine, 2-(N,N-diethylamino)ethylamine, 3-(N,N-dimathylamino)propylamine, 3-(N,N-diethylamino)propylamine, benzylamine, 2-phenylethylamine, 3-phenylpropylamine, aniline, 2-hydroxyaniline, 3-hydroxyaniline, 4-hydroxyaniline, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, 2-chloroaniline, 3-chloroaniline, 3-nitroaniline, 4-nitroaniline, o-toluidine, m-toluidine, p-toluidine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2-trifluoromethylaniline, 3-trifluoromethylaniline, 4-trifluoromethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, glycine methyl ester, glycine ethyl ester, glycine propyl ester, glycine butyl ester, hydrazine, N,N-dimethylhydrazine or phenylhydrazine.

Examples of T⁴ are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy or hexyloxy.

The radical T⁶ is derived, for example, from an active methylene compound of the formula H₂ T⁶. Examples of formulae of these compounds are ##STR9## where Z is cyano, nitro, C₁ -C₆ -alkanoyl, benzoyl, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, carboxyl, C₁ -C₄ -alkoxycarbonyl, carbamoyl or mono- or di-C₁ -C₄ -alkylcarbamoyl, or ##STR10##

Examples of some particularly important compounds are: ##STR11##

Examples of Y are methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, pentylamino, isopentylamino, neopentylamino, hexylamino, heptylamino, octylamino, isooctylamino, 2-ethylhexylamino, nonylamino, isononylamino, decylamino, isodecylamino, undecylamino, dodecylamino, tridecylamino, isotridecylamino, tetradecylamino, pentadecylamino, hexadecylamino, heptadecylamino, octadecylamino, nonadecylamino, eicosylamino, (R)-(-)-1-cyclohexylethylamino, (S)-(+)-1-cyclohexylethylamino, 2-cyclohexylethylamino, 2-hydroxyethylamino, 2-methoxyethylamino, 2-ethoxyethylamino, 2-phenoxyethylamino, 2-(2-hydroxyethoxy)ethylamino, 2-(2-hydroxyethyl)aminoethylamino, 2-aminoethylamino, 2-dimethylaminoethylamino, 2-diethylaminoethylamino, 2-diisopropylaminoethylamino, 2-(1-piperazinyl)ethylamino, 3-hydroxy-n-propylamino, 3-methoxy-n-propylamino, 3-ethoxy-n-propylamino, 3-isopropoxy-n-propylamino, 3-phenoxy-n-propylamino, 3-benzyloxy-n-propylamino, 3-(2-methoxyethoxy)-n-propylamino, 3-(2-ethoxyethoxy)-n-propylamino, 3-(2-phenoxyethoxy)-n-propylamino, 3-amino-n-propylamino, 3-dimethylamino-n-propylamino, 3-diethylamino-n-propylamino, 3-di-n-propylamino-n-propylamino, 3-diisopropylamino-n-propylamino, 3-di-n-butylamino-n-propylamino, 3-morpholino-n-propylamino, 4-hydroxy-n-butylamino, 4-amino-n-butylamino, 5-hydroxy-n-pentylamino, 5-amino-n-pentylamino, 6-hydroxy-n-hexylamino, 6-amino-n-hexylamino, 7-hydroxy-n-heptylamino, 7-amino-n-heptylamino, 8-hydroxy-n-octylamino, 8-amino-n-octylamino, 9-hydroxy-n-nonylamino, 9-amino-n-nonylamino, 10-hydroxy-n-decylamino, 10-amino-n-decylamino, 11-amino-n-undecylamino, 4-diethylamino-1-methyl-n-butylamino, 2-hydroxy-n-propylamino,1-ethyl-2-hydroxyethylamino, 2-hydroxy-1,1-dimethylethylamino, 1,1-bis(hydroxymethyl)ethylamino, 1-ethyl-2-hydroxyethylamino, 2-carboxyethylamino, 3-carboxy-n-propylamino, 4-carboxy-n-butylamino, 5-carboxy-n-pentylamino, 10-carboxy-n-decylamino, phenylamino, o-methylphenylamino, m-methylphenylamino, p-methylphenylamino, o-ethylphenylamino, m-ethylphenylamino, p-ethylphenylamino, o-trifluoromethylphenylamino, m-trifluoromethylphenylamino, p-trifluoromethylphenylamino, o-hydroxyphenylamino, m-hydroxyphenylamino, p-hydroxyphenylamino, o-methoxyphenylamino, m-methoxyphenylamino, p-mathoxyphenylamino, o-ethoxyphenylamino, m-ethoxyphenylamino, p-ethoxyphenylamino, o-chlorophenylamino, m-chlorophenylamino, p-chlorophenylamino, o-fluorophenylamino, m-fluorophenylamino, p-fluorophenylamino, o-bromophenylamino, m-bromophenylamino, p-bromophenylamino, o-iodophenylamino, m-iodophenylamino, p-iodophenylamino, o-aminophenylamino, m-aminophenylamino, p-aminophenylamino, p-acetylaminophenylamino, o-hydroxymethylphenylamino, m-hydroxymethylphenylamino, p-hydroxymethylphenylamino, o-carboxyphenylamino, m-carboxyphenylamino, p-carboxyphenylamino, o-aminocarbonylphenylamino, m-aminocarbonylphenylamino, p-aminocarbonylphenylamino, o-cyanophenylamino, m-cyanophenylamino, p-cyanophenylamino, 2,6-dimethylphenylamino, 3,5-dimethylphenylamino, 2-hydroxy-5-methylphenylamino, 2-hydroxy-4-methylphenylamino, 4-hydroxy-2-methylphenylamino, 2-hydroxy-5-chlorophenylamino, 1-imidazolyl, 1-pyrazolyl, 2-pyridylamino, 3-pyridylamino, 4-pyridylamino, 3-pyridylmethylamino, 2-furylmethylamino, thienylamino, benzylamino, o-methoxybenzylamino, p-methoxybenzylamino, p-fluorobenzylamino, o-chlorobenzylamino, p-chlorobenzylamino, 3,4-dimethoxybenzylamino, 2-phenylethylamino, (+/-)-α-methylbenzylamino, (+)-α-methylbenzylamino, (-)-α-methylbenzylamino, 3-phenyl-n-propylamino, 1-methyl-3-phenyl-n-propylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, cyclooctylamino, cyclononylamino, cyclodecylamino, cyclododecylamino, allylamino, propargylamino, methallylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, diisopropylamino, diisobutylamino, di-sec-butylamino, di-n-pentylamino, diisopentylamino, di-n-hexylamino, di-(2-ethylhexyl)amino, di-n-octylamino, diallylamino, dicyclohexylamino, N-methyl-n-butylamino, N-methylcyclohexylamino, N-ethylcyclohexylamino, N-methylethanolamino, N-ethyl-1,3-dimethyl-n-propylamino, N-ethylethanolamino, N-ethyl-2-hydroxy-n-propylamino, N-tert-butylethanolamino, N-methylphenylamino, N-ethylphenylamino, N-n-propylphenylamino, N-isopropylphenylamino, N-n-butylphenylamino, dibenzylamino, N-methylbenzylamino, N-ethylbenzylamino, N-isopropylbenzylamino, N-tert-butylbenzylamino, N-(2-hydroxyethyl)benzylamino, N-phenylbenzylamino, N-benzyl-2-phenylethylamino, pyrrolidino, piperidino, hexamethyleneimino, morpholino, N-methylpiperazino, piperazino, N-ethylpiperazino or thiomorpholino.

Examples of R³ are mercapto, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, hexylthio, heptylthio, octylthio, 2-ethylhexylthio, benzylthio, 1- or 2-phenylethylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, allylthio, methallylthio, propargylthio, phenylthio, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, hexylsulfinyl, heptylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, benzylsulfinyl, 1- or 2-phenylethylsulfinyl, cyclopentylsulfinyl, cyclohexylsulfinyl, cycloheptylsulfinyl, allylsulfinyl, methallylsulfinyl, propargylsulfinyl, phenylsulfinyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, benzylsulfonyl, 1- or 2-phenylethylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, cycloheptylsulfonyl, allylsulfonyl, methallylsulfonyl, propargylsulfonyl or phenylsulfonyl.

Preferred aminothiazoles of the formula I are those in which R¹ and R² are each hydrogen or together form the radical ##STR12## where T¹ is hydrogen, C₁ -C₄ -alkyl or phenyl and T² and T³ are each, independently of one another, C₁ -C₄ -alkyl or phenyl, or form, together with the nitrogen atom connecting them, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)piperazino or hexamethyleneimino, and R³ and R⁴ each has the abovementioned meanings.

Particularly preferred aminothiazoles of the formula I are those in which R¹ and R² are each hydrogen or together form the radical ##STR13## where T¹ is hydrogen and T² and T³ are each, independently of one another, C₁ -C₄ -alkyl.

Further particularly preferred aminothiazoles of the formula I are those in which R⁴ is formyl, acetyl, propionyl, butyryl, benzoyl, cyano or ##STR14## where T⁵ is hydrogen, methyl, ethyl or phenyl, and T⁴ and T⁶ each has the abovementioned meanings.

Further particularly preferred aminothiazoles of the formula I are those in which Y is mono- or di-C₁ -C₆ -alkylamino, allylamino, methallylamino, propargylamino, C₂ -C₆ -alkylamino which is substituted by phenyl, hydroxyl, phenoxy, amino or mono- or di-C₁ -C₄ -alkylamino or interrupted by an oxygen atom, or phenylamino, pyrrolidino, piperidino, morpholino, piperazino or N-(C₁ -C₄ -alkyl)piperazino.

Further particularly preferred aminothiazoles of the formula I are those in which R³ is C₁ -C₆ -alkylthio, benzylthio, cyclohexylthio, C₃ -C₄ -alkenylthio, propargy thio, phenylthio, C₁ -C₆ -alkylsulfonyl, benzylsulfonyl, cyclohexylsulfonyl, C₃ -C₄ -alkenylsulfonyl, propargylsulfonyl or phenylsulfonyl.

Further particularly preferred aminothiazoles of the formula I are those in which R⁴ is cyano, formyl or ##STR15## where Z is cyano, nitro or C₁ -C₄ -alkoxycarbonyl.

Particularly important aminothiazoles of the formula I are those in which R¹ and R² are each hydrogen or together form the radical ═CH--N(CH₃)₂.

Further particularly noteworthy aminothiazoles of the formula I are those in which R⁴ is formyl, cyano or ##STR16## where T⁴ is hydroxyl, methoxy, ethoxy or amino, T⁵ is hydrogen, methyl, ethyl or phenyl and T⁶ has the abovementioned meanings.

Attention is drawn to aminothiazoles of the formula I in which R⁴ is formyl, cyano or ##STR17## where T⁶ has the abovementioned meanings.

Particular attention is drawn to aminothiazoles of the formula Ia ##STR18## or the tautomers thereof, where

L¹ is amino,

L² is C₁ -C₆ -alkylthio, benzylthio, cyclohexylthio, C₃ -C₄ -alkenylthio, propargylthio, phenylthio, C₁ -C₆ -alkylsulfonyl, benzylsulfonyl, cyclohexylsulfonyl, C₃ -C₄ -alkenylsulfonyl, propargylsulfonyl, phenylsulfonyl, mono- or di-C₁ -C₆ -alkylamino, allylamino, methallylamino, propargylamino, C₂ -C₆ -alkylamino which is substituted by phenyl, hydroxyl, phenoxy, amino or mono- or di-C₁ -C₄ -alkylamino or interrupted by an oxygen atom, or phenylamino, pyrrolidino, piperidino, morpholino, piperazino or N-(C₁ -C₄ -alkyl)piperazino and

L³ is cyano, formyl or the radical ##STR19## where Z is cyano, nitro or C₁ -C₄ -alkoxycarbonyl.

Particular industrial importance attaches to aminothiazoles of the formula I where n is 0 or 2 and X is benzyl or phenyl.

The aminothiazoles of the formula I according to the invention can be obtained, for example, by reacting haloaminothiazoles of the formula II ##STR20## where R¹, R² and R⁴ each has the abovementioned meanings, and Hal is chlorine or bromine, with a compound of the formula III

    R.sup.3 --H                                                (III)

where R³ has the abovementioned meanings. If R³ is --S(O)_(n) --X, the compounds are generally used in the form of their alkali metal salts.

For example, the haloaminothiazole II is reacted with the compound III (or its alkali metal salt) in an inert solvent (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, 1,3-dimethylhexahydro-2-pyrimidone, 1,2-diethoxyethane, benzene, toluene, xylene, methylene chloride, chloroform, methanol, ethanol, propanol, isopropanol, butanol or isobutanol) at from -10° to +150° C., where appropriate in the presence of a base (e.g. triethylamine, tripropylamine, tributylamine, pyridine, 4-dimethylaminopyridine, sodium methylate, sodium ethylate, potassium tert-butylate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, sodium hydride or potassium hydride). The molar ratio of II:III is usually from 1:2 to 1:10. When the reaction is carried out in the presence of a base, the molar ratio of base to III is generally from 1:1 to 10:1.

The presence of a base is expedient for the reaction of compounds of the formula III where R³ is --S(O)_(n) --X.

The haloaminothiazoles of the formula II are known and described, for example, in U.S. Pat. No. 4,395,544 or can be obtained by methods similar to those detailed therein.

The novel aminothiazoles are valuable intermediates for the synthesis of dyes, crop protection agents or pharmaceuticals. They are used in particular as diazo components (R¹, R² ═H) or precursors thereof for preparing azo dyes.

For preparing azo dyes the amino compound of the formula IV ##STR21## where R³ and R⁴ have the above mentioned meanings, can for example be reacted in an acidic aqueous medium with an alkali nitrite to give a diazonium salt of the formula IVa ##STR22## where An⊖ is an anion (e.g., chloride) and R³ and R⁴ have the abovementioned meanings, which in turn can be coupled with a coupling component of the formula V

    H--K                                                       (V),

where K is the radical of a coupling compoent (e.g., dimethyl aniline) to yield an azo dye of the formula VI ##STR23## where R³, R⁴ and K have the above meanings.

Precursors of the amino compounds IV are thiazoles of the formula IVb ##STR24## where R³, R⁴, T¹, T² and T³ have the above meanings, which are easily converted to the amino compound by hydrolysis.

The Examples which follow are intended to illustrate the invention in detail.

EXAMPLE 1

3.7 g of sodium ethanolate were dissolved in 40 ml of ethanol. To this were added 4.5 g of n-butanethiol, and the mixture was stirred at room temperature for 15 minutes. Then 8.1 g of 2-amino-4-chloro-5-formylthiazole were added and the mixture was stirred at room temperature for 2 hours. The solvent was then removed by distillation under reduced pressure, and the residue was stirred with 150 ml of hot water. The suspension was adjusted to pH 3 with concentrated hydrochloric acid, cooled to 10° C. and stirred at this temperature for a further 2 hours. The precipitate was filtered off with suction, washed with water and dried in a vacuum oven at 50° C. It was purified by recrystallization from a mixture of water and acetic acid with the addition of active carbon. 8.1 g (75% of theory) of the compound of the formula ##STR25## were obtained of melting point 131° to 132° C. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the indicated structure.

EXAMPLE 2

16.25 g of 2-amino-4-chloro-5-formylthiazole were dissolved in 100 ml of N,N-dimethylformamide. To this were added 19.6 g of sodium benzenesulfinate. The mixture was stirred at room temperature for one hour and at 70° C. for 4 hours. The mixture was then poured into 600 ml of ice-water, and the precipitate was filtered off with suction, washed with water and dried at 50° C. under reduced pressure. 21.6 g (81% of theory) of the compound ##STR26## were obtained of melting point 166° to 167° C. The IR, NMR, UV and mass spectra and the elemental analysis are consistent with the indicated formula.

The compounds of the formula ##STR27## which are listed in Table 1 which follows can be prepared in a similar manner.

                                      TABLE 1                                      __________________________________________________________________________                                            Melting                                 Example                                point                                   no.  R.sup.3   NR.sup.1 R.sup.2                                                                         R.sup.4       (°C.)                            __________________________________________________________________________      3   SH        NH.sub.2  CHO                                                    4   S--CH.sub.3                                                                              NH.sub.2  CHO                                                    5   S--C.sub.2 H.sub.5                                                                       NH.sub.2  CHO                                                    6   S-nC.sub.3 H.sub.7                                                                       NH.sub.2  CHO           124-124.5                                7   S-isoC.sub.3 H.sub.7                                                                     NH.sub.2  CHO                                                    8   S-isoC.sub.4 H.sub.9                                                                     NH.sub.2  CHO                                                    9   S-secC.sub.4 H.sub.9                                                                     NH.sub.2  CHO                                                    10  S-tertC.sub.4 H.sub.9                                                                    NH.sub.2  CHO                                                    11  S-nC.sub.5 H.sub.11                                                                      NH.sub.2  CHO                                                    12  S-neoC.sub.5 H.sub.11                                                                    NH.sub.2  CHO                                                    13  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CHO           123-125                                  14  S-nC.sub.7 H.sub.15                                                                      NH.sub.2  CHO                                                    15  S-nC.sub.8 H.sub.17                                                                      NH.sub.2  CHO           106-107                                  16  S-nC.sub.9 H.sub.19                                                                      NH.sub.2  CHO                                                    17  S-nC.sub.10 H.sub.21                                                                     NH.sub.2  CHO                                                    18  S-nC.sub.11 H.sub.23                                                                     NH.sub.2  CHO                                                    19  S-nC.sub.12 H.sub.25                                                                     NH.sub.2  CHO                                                    20  S-nC.sub.13 H.sub.27                                                                     NH.sub.2  CHO                                                    21  S-nC.sub.14 H.sub.29                                                                     NH.sub.2  CHO                                                    22  S-nC.sub.15 H.sub.31                                                                     NH.sub.2  CHO                                                    23  S-nC.sub.16 H.sub.33                                                                     NH.sub.2  CHO                                                    24  S-nC.sub.17 H.sub.35                                                                     NH.sub.2  CHO                                                    25  S-nC.sub.18 H.sub.37                                                                     NH.sub.2  CHO                                                    26  S-nC.sub.19 H.sub.39                                                                     NH.sub.2  CHO                                                    27  S-nC.sub.20 H.sub.41                                                                     NH.sub.2  CHO                                                    28  S-Cyclopropyl                                                                            NH.sub.2  CHO                                                    29  S-Cyclopentyl                                                                            NH.sub.2  CHO                                                    30  S-Cyclohexyl                                                                             NH.sub.2  CHO           162-163.5                                31  S-Cycloheptyl                                                                            NH.sub.2  CHO                                                    32  S-Cyclooctyl                                                                             NH.sub.2  CHO                                                    33  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CHO           174-175                                  34  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CHO           153-155                                  35  S--(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                                    NH.sub.2  CHO                                                    36  S--CH.sub.2 CH.sub.2 OH                                                                  NH.sub.2  CHO                                                    37  S--CH.sub.2 --CH═CH.sub.2                                                            NH.sub.2  CHO                                                    38  S--CH.sub.2 --C.tbd.CH                                                                   NH.sub.2  CHO                                                    39  SH        NH.sub.2  CN                                                     40  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CN                                                     41  S-nC.sub.3 H.sub.7                                                                       NH.sub.2  CN                                                     42  S-isoC.sub.3 H.sub.7                                                                     NH.sub.2  CN                                                     43  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CN                                                     44  S-isoC.sub.4 H.sub.9                                                                     NH.sub.2  CN                                                     45  S-secC.sub.4 H.sub.9                                                                     NH.sub.2  CN                                                     46  S-tertC.sub.4 H.sub.9                                                                    NH.sub.2  CN                                                     47  S-nC.sub.5 H.sub.11                                                                      NH.sub.2  CN                                                     48  S-neoC.sub.5 H.sub.11                                                                    NH.sub.2  CN                                                     49  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CN                                                     50  S-nC.sub.7 H.sub.15                                                                      NH.sub.2  CN                                                     51  S-nC.sub.8 H.sub.17                                                                      NH.sub.2  CN                                                     52  S-nC.sub.9 H.sub.19                                                                      NH.sub.2  CN                                                     53  S-nC.sub.10 H.sub.21                                                                     NH.sub.2  CN                                                     54  S-nC.sub.11 H.sub.23                                                                     NH.sub.2  CN                                                     55  S-nC.sub.12 H.sub.23                                                                     NH.sub.2  CN                                                     56  S-nC.sub.13 H.sub.25                                                                     NH.sub.2  CN                                                     57  S-nC.sub.14 H.sub.29                                                                     NH.sub.2  CN                                                     58  S-nC.sub.15 H.sub.31                                                                     NH.sub.2  CN                                                     59  S-nC.sub.16 H.sub.33                                                                     NH.sub.2  CN                                                     60  S-nC.sub.17 H.sub.35                                                                     NH.sub.2  CN                                                     61  S-nC.sub.18 H.sub.37                                                                     NH.sub.2  CN                                                     62  S-nC.sub.19 H.sub.39                                                                     NH.sub.2  CN                                                     63  S-nC.sub.20 H.sub.41                                                                     NH.sub.2  CN                                                     64  S-Cyclopropyl                                                                            NH.sub.2  CN                                                     65  S-Cyclopentyl                                                                            NH.sub.2  CN                                                     66  S-Cyclohexyl                                                                             NH.sub.2  CN                                                     67  S-Cycloheptyl                                                                            NH.sub.2  CN                                                     68  S-Cyclooctyl                                                                             NH.sub.2  CN                                                     69  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CN                                                     70  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CN                                                     71  S--(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                                    NH.sub.2  CN                                                     72  S--CH.sub.2 CH.sub.2 OH                                                                  NH.sub.2  CN                                                     73  S--CH.sub.2 --CH═CH.sub.2                                                            NH.sub.2  CN                                                     74  S--CH.sub.2 --C.tbd.CH                                                                   NH.sub.2  CN                                                     75  S--CH.sub.2 --C(CH.sub.3)═CH.sub.2                                                   NH.sub.2  CHO                                                    76  SO.sub.2 --CH.sub.3                                                                      NH.sub.2  CHO                                                    77  SO.sub.2 --C.sub.2 H.sub.5                                                               NH.sub.2  CHO                                                    78  SO.sub.2 -nC.sub.3 H.sub.7                                                               NH.sub.2  CHO                                                    79  SO.sub.2 -isoC.sub.3 H.sub.7                                                             NH.sub.2  CHO                                                    80  SO.sub.2 -nC.sub.4 H.sub.9                                                               NH.sub.2  CHO                                                    81  SO.sub.2 -isoC.sub.4 H.sub.9                                                             NH.sub.2  CHO                                                    82  SO.sub.2 -secC.sub.4 H.sub.9                                                             NH.sub.2  CHO                                                    83  SO.sub.2 -tertC.sub.4 H.sub.9                                                            NH.sub.2  CHO                                                    84  SO.sub. 2 -nC.sub.5 H.sub.11                                                             NH.sub.2  CHO                                                    85  SO.sub.2 -neoC.sub.5 H.sub.11                                                            NH.sub.2  CHO                                                    86  SO.sub.2 -nC.sub.6 H.sub.13                                                              NH.sub.2  CHO                                                    87  SO.sub.2 -nC.sub.7 H.sub.15                                                              NH.sub.2  CHO                                                    88  SO.sub.2 -nC.sub.8 H.sub.17                                                              NH.sub.2  CHO                                                    89  SO.sub.2 -nC.sub.9 H.sub.19                                                              NH.sub.2  CHO                                                    90  SO.sub.2 -nC.sub.10 H.sub.21                                                             NH.sub.2  CHO                                                    91  SO.sub.2 -nC.sub.11 H.sub.23                                                             NH.sub.2  CHO                                                    92  SO.sub.2 -nC.sub.12 H.sub.25                                                             NH.sub.2  CHO                                                    93  SO.sub.2 -nC.sub.13 H.sub.27                                                             NH.sub.2  CHO                                                    94  SO.sub.2 -nC.sub.14 H.sub.29                                                             NH.sub.2  CHO                                                    95  SO.sub.2 -nC.sub.15 H.sub.31                                                             NH.sub.2  CHO                                                    96  SO.sub.2 -nC.sub.16 H.sub.33                                                             NH.sub.2  CHO                                                    97  SO.sub.2 -nC.sub.17 H.sub.35                                                             NH.sub.2  CHO                                                    98  SO.sub.2 -nC.sub.18 H.sub.37                                                             NH.sub.2  CHO                                                    99  SO.sub.2 -nC.sub.19 H.sub.39                                                             NH.sub.2  CHO                                                   100  SO.sub.2 -nC.sub.20 H.sub.41                                                             NH.sub.2  CHO                                                   101  SO.sub.2 -Cyclopropyl                                                                    NH.sub.2  CHO                                                   102  SO.sub.2 -Cyclopentyl                                                                    NH.sub.2  CHO                                                   103  SO.sub.2 -Cyclohexyl                                                                     NH.sub.2  CHO                                                   104  SO.sub.2 -Cycloheptyl                                                                    NH.sub.2  CHO                                                   105  SO.sub.2 -Cyclooctyl                                                                     NH.sub.2  CHO                                                   106  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CH═C(CN)  (COOC.sub.2 H.sub.5)                    107  SO.sub.2 --CH.sub.2 C.sub.6 H.sub.5                                                      NH.sub.2  CHO                                                   108  SO.sub.2 --(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                            NH.sub.2  CHO                                                   109  SO.sub.2 --CH.sub.2 CH.sub.2 OH                                                          NH.sub.2  CHO                                                   110  SO.sub.2 --CH.sub.2 --CH═CH.sub.2                                                    NH.sub.2  CHO                                                   111  SO.sub.2 --CH.sub.2 --C.tbd.CH                                                           NH.sub.2  CHO                                                   112  S--CH.sub.2 --C(CH.sub.3)═CH.sub.2                                                   NH.sub.2  CN                                                    113  SO.sub.2 --CH.sub.3                                                                      NH.sub.2  CN                                                    114  SO.sub.2 --C.sub.2 H.sub.5                                                               NH.sub.2  CN                                                    115  SO.sub.2 --nC.sub.3 H.sub.7                                                              NH.sub.2  CN                                                    116  SO.sub.2 --isoC.sub.3 H.sub.7                                                            NH.sub.2  CN                                                    117  SO.sub.2 --nC.sub.4 H.sub.9                                                              NH.sub.2  CN                                                    118  SO.sub.2 -isoC.sub.4 H.sub.9                                                             NH.sub.2  CN                                                    119  SO.sub.2 -secC.sub.4 H.sub.9                                                             NH.sub.2  CN                                                    120  SO.sub.2 -tertC.sub.4 H.sub.9                                                            NH.sub.2  CN                                                    121  SO.sub.2 -nC.sub.5 H.sub.11                                                              NH.sub.2  CN                                                    122  SO.sub.2 -neoC.sub.5 H.sub.11                                                            NH.sub.2  CN                                                    123  SO.sub.2 -nC.sub.6 H.sub.13                                                              NH.sub.2  CN                                                    124  SO.sub.2 -nC.sub.7 H.sub.15                                                              NH.sub.2  CN                                                    125  SO.sub.2 -nC.sub.8 H.sub.17                                                              NH.sub.2  CN                                                    126  SO.sub.2 -nC.sub.9 H.sub.19                                                              NH.sub.2  CN                                                    127  SO.sub.2 -nC.sub.10 H.sub.21                                                             NH.sub.2  CN                                                    128  SO.sub.2 -nC.sub.11 H.sub.23                                                             NH.sub.2  CN                                                    129  SO.sub.2 -nC.sub.12 H.sub.25                                                             NH.sub.2  CN                                                    130  SO.sub.2 -nC.sub.13 H.sub.27                                                             NH.sub.2  CN                                                    131  SO.sub.2 -nC.sub.14 H.sub.29                                                             NH.sub.2  CN                                                    132  SO.sub.2 -nC.sub.15 H.sub.31                                                             NH.sub.2  CN                                                    133  SO.sub.2 -nC.sub.16 H.sub.33                                                             NH.sub.2  CN                                                    134  SO.sub.2 -nC.sub.17 H.sub.35                                                             NH.sub.2  CN                                                    135  SO.sub.2 -nC.sub.18 H.sub.37                                                             NH.sub.2  CN                                                    136  SO.sub.2 -nC.sub.19 H.sub.39                                                             NH.sub.2  CN                                                    137  SO.sub.2 -nC.sub.20 H.sub.41                                                             NH.sub.2  CN                                                    138  SO.sub.2 -Cyclopropyl                                                                    NH.sub.2  CN                                                    139  SO.sub.2 -Cyclopentyl                                                                    NH.sub.2  CN                                                    140  SO.sub.2 -Cyclohexyl                                                                     NH.sub.2  CN                                                    141  SO.sub.2 -Cycloheptyl                                                                    NH.sub.2  CN                                                    142  SO.sub.2 -Cyclooctyl                                                                     NH.sub. 2 CN                                                    143  SO.sub.2 -C.sub.6 H.sub.5                                                                NH.sub.2  CN                                                    144  SO.sub.2 --CH.sub.2 C.sub.6 H.sub.5                                                      NH.sub.2  CN                                                    145  SO.sub.2 --(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                            NH.sub.2  CN                                                    146  SO.sub.2 CH.sub.2 CH.sub.2 OH                                                            NH.sub.2  CN                                                    147  SO.sub.2 --CH.sub.2 --CH═CH.sub.2                                                    NH.sub.2  CN                                                    148  SO.sub.2 --CH.sub.2 --C.tbd.CH.sub.2                                                     NH.sub.2  CN                                                    149  SH        NH.sub.2  COOH                                                  150  S--CH.sub.3                                                                              NH.sub.2  COOH                                                  151  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COOH                                                  152  S-nC.sub.3 H.sub.7                                                                       NH.sub.2  COOH                                                  153  S-isoC.sub.3 H.sub.7                                                                     NH.sub.2  COOH                                                  154  S-isoC.sub.4 H.sub.9                                                                     NH.sub.2  COOH                                                  155  S-secC.sub.4 H.sub.9                                                                     NH.sub.2  COOH                                                  156  S-tertC.sub.4 H.sub.9                                                                    NH.sub.2  COOH                                                  157  S-nC.sub.5 H.sub.11                                                                      NH.sub.2  COOH                                                  158  S-neoC.sub.5 H.sub.11                                                                    NH.sub.2  COOH                                                  159  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  COOH                                                  160  S-nC.sub.7 H.sub.15                                                                      NH.sub.2  COOH                                                  161  S-nC.sub.8 H.sub.17                                                                      NH.sub.2  COOH                                                  162  S-nC.sub.9 H.sub.19                                                                      NH.sub.2  COOH                                                  163  S-nC.sub.10 H.sub.21                                                                     NH.sub.2  COOH                                                  164  S-nC.sub.11 H.sub.23                                                                     NH.sub.2  COOH                                                  165  S-nC.sub.12 H.sub.25                                                                     NH.sub.2  COOH                                                  166  S-nC.sub.13 H.sub.27                                                                     NH.sub.2  COOH                                                  167  S-nC.sub.14 H.sub.29                                                                     NH.sub.2  COOH                                                  168  S-nC.sub.15 H.sub.31                                                                     NH.sub.2  COOH                                                  169  S-nC.sub.16 H.sub.33                                                                     NH.sub.2  COOH                                                  170  S-nC.sub.17 H.sub.35                                                                     NH.sub.2  COOH                                                  171  S-nC.sub.18 H.sub.37                                                                     NH.sub.2  COOH                                                  172  S-nC.sub.20 H.sub.39                                                                     NH.sub.2  COOH                                                  173  S-nC.sub.20 H.sub.41                                                                     NH.sub.2  COOH                                                  174  S-Cyclopropyl                                                                            NH.sub.2  COOH                                                  175  S-Cyclopentyl                                                                            NH.sub.2  COOH                                                  176  S-Cyclohexyl                                                                             NH.sub.2  COOH                                                  177  S-Cycloheptyl                                                                            NH.sub.2  COOH                                                  178  S-Cyclooctyl                                                                             NH.sub.2  COOH                                                  179  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COOH                                                  180  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COOH                                                  181  S--(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                                    NH.sub.2  COOH                                                  182  S--CH.sub.2 CH.sub.2 OH                                                                  NH.sub.2  COOH                                                  183  S--CH.sub.2 --CH═CH.sub.2                                                            NH.sub.2  COOH                                                  184  S--CH.sub.2 --C.tbd.CH                                                                   NH.sub.2  COOH                                                  185  SH        NH.sub.2  COOCH.sub.3                                           186  S--CH.sub.3                                                                              NH.sub.2  COOCH.sub.3                                           187  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COOCH.sub.3                                           188  S-nC.sub.3 H.sub.7                                                                       NH.sub.2  COOCH.sub.3                                           189  S-isoC.sub. 3 H.sub.7                                                                    NH.sub.2  COOCH.sub.3                                           190  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  COOCH.sub.3                                           191  S-isoC.sub.4 H.sub.9                                                                     NH.sub.2  COOCH.sub.3                                           102  S-secC.sub.4 H.sub.9                                                                     NH.sub.2  COOCH.sub.3                                           193  S-tertC.sub.4 H.sub.9                                                                    NH.sub.2  COOCH.sub.3                                           194  S-nC.sub.5 H.sub.11                                                                      NH.sub.2  COOCH.sub.3                                           195  S-neoC.sub.5 H.sub.11                                                                    NH.sub.2  COOCH.sub.3                                           196  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  COOCH.sub.3                                           197  S-nC.sub.7 H.sub.15                                                                      NH.sub.2  COOCH.sub.3                                           198  S-nC.sub.8 H.sub.17                                                                      NH.sub.2  COOCH.sub.3                                           199  S-nC.sub.9 H.sub.19                                                                      NH.sub.2  COOCH.sub.3                                           200  S-nC.sub.10 H.sub.21                                                                     NH.sub.2  COOCH.sub.3                                           201  S-nC.sub.11 H.sub.23                                                                     NH.sub.2  COOCH.sub.3                                           202  S-nC.sub.12 H.sub.25                                                                     NH.sub.2  COOCH.sub.3                                           203  S-nC.sub.13 H.sub.27                                                                     NH.sub.2  COOCH.sub.3                                           204  S-nC.sub.14 H.sub.29                                                                     NH.sub.2  COOCH.sub.3                                           205  S-nC.sub.15 H.sub.31                                                                     NH.sub.2  COOCH.sub.3                                           206  S-nC.sub.16 H.sub.33                                                                     NH.sub.2  COOCH.sub.3                                           207  S-nC.sub.17 H.sub.35                                                                     NH.sub.2  COOCH.sub.3                                           208  S-nC.sub.18 H.sub.37                                                                     NH.sub.2  COOCH.sub.3                                           209  S-nC.sub.19 H.sub.39                                                                     NH.sub.2  COOCH.sub.3                                           210  S-nC.sub.20 H.sub.41                                                                     NH.sub.2  COOCH.sub.3                                           211  S-Cyclopropyl                                                                            NH.sub.2  COOCH.sub.3                                           212  S-Cyclopentyl                                                                            NH.sub.2  COOCH.sub.3                                           213  S-Cyclohexyl                                                                             NH.sub.2  COOCH.sub.3                                           214  S-Cycloheptyl                                                                            NH.sub.2  COOCH.sub.3                                           215  S-Cyclooctyl                                                                             NH.sub.2  COOCH.sub.3                                           216  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COOCH.sub.3                                           217  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COOCH.sub.3                                           218  S--(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                                    NH.sub.2  COOCH.sub.3                                           219  S--CH.sub.2 CH.sub.2 OH                                                                  NH.sub.2  COOCH.sub.3                                           220  S--CH.sub.2 --CH═CH.sub.2                                                            NH.sub.2  COOCH.sub.3                                           221  S--CH.sub.2 --C.tbd.CH                                                                   NH.sub.2  COOCH.sub.3                                           222  S--CH.sub.2 --C(CH.sub.3)═CH.sub.2                                                   NH.sub.2  COOH                                                  223  SO.sub.2 --CH.sub.3                                                                      NH.sub.2  COOH                                                  224  SO.sub.2 --C.sub.2 H.sub.5                                                               NH.sub.2  COOH                                                  225  SO.sub.2 -nC.sub.3 H.sub.7                                                               NH.sub.2  COOH                                                  226  SO.sub.2 -isoC.sub.3 H.sub.7                                                             NH.sub.2  COOH                                                  227  SO.sub.2 -nC.sub.4 H.sub.9                                                               NH.sub.2  COOH                                                  228  SO.sub.2 -isoC.sub.4 H.sub.9                                                             NH.sub.2  COOH                                                  229  SO.sub.2 -secC.sub.4 H.sub.9                                                             NH.sub.2  COOH                                                  230  SO.sub.2 -tertC.sub.4 H.sub.9                                                            NH.sub.2  COOH                                                  231  SO.sub.2 -nC.sub.5 H.sub.11                                                              NH.sub.2  COOH                                                  232  SO.sub.2 -neoC.sub.5 H.sub.11                                                            NH.sub.2  COOH                                                  233  SO.sub.2 -nC.sub.6 H.sub.13                                                              NH.sub.2  COOH                                                  234  SO.sub.2 -nC.sub.7 H.sub.15                                                              NH.sub.2  COOH                                                  235  SO.sub.2 -nC.sub.8 H.sub.17                                                              NH.sub.2  COOH                                                  236  SO.sub.2 -nC.sub.9 H.sub.21                                                              NH.sub.2  COOH                                                  237  SO.sub.2 -nC.sub.10 H.sub.21                                                             NH.sub.2  COOH                                                  238  SO.sub.2 -nC.sub.11 H.sub.23                                                             NH.sub.2  COOH                                                  239  SO.sub.2 -nC.sub.12 H.sub.25                                                             NH.sub.2  COOH                                                  240  SO.sub.2 -nC.sub.13 H.sub.27                                                             NH.sub.2  COOH                                                  241  SO.sub.2 -nC.sub.14 H.sub.29                                                             NH.sub.2  COOH                                                  242  SO.sub.2 -nC.sub.15 H.sub.31                                                             NH.sub.2  COOH                                                  243  SO.sub.2 -nC.sub.16 H.sub.33                                                             NH.sub.2  COOH                                                  244  SO.sub.2 -nC.sub.17 H.sub.35                                                             NH.sub.2  COOH                                                  245  SO.sub.2 -nC.sub.18 H.sub.37                                                             NH.sub.2  COOH                                                  246  SO.sub.2 -nC.sub.19 H.sub.39                                                             NH.sub.2  COOH                                                  247  SO.sub.2 -nC.sub.20 H.sub.41                                                             NH.sub.2  COOH                                                  248  S-Cyclopropyl                                                                            NH.sub.2  COOH                                                  249  S-Cyclopentyl                                                                            NH.sub.2  COOH                                                  250  S-Cyclophexyl                                                                            NH.sub.2  COOH                                                  251  S-Cycloheptyl                                                                            NH.sub.2  COOH                                                  252  S-Cyclooctyl                                                                             NH.sub.2  COOH                                                  253  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COOH                                                  254  SO.sub.2 -- CH.sub.2 C.sub.6 H.sub.5                                                     NH.sub.2  COOH                                                  255  SO.sub.2 --(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                            NH.sub.2  COOH                                                  256  SO.sub.2 --CH.sub.2 CH.sub.2 OH                                                          NH.sub.2  COOH                                                  257  SO.sub.2 --CH.sub.2 --CH═CH.sub.2                                                    NH.sub.2  COOH                                                  258  SO.sub.2 --CH.sub.2 --C.tbd.CH                                                           NH.sub.2  COOH                                                  259  S--CH.sub.2 --C(CH.sub.3)═CH.sub.2                                                   NH.sub.2  COOCH.sub.3                                           260  SO.sub.2 --CH.sub.3                                                                      NH.sub.2  COOCH.sub.3                                           261  SO.sub.2 --C.sub.2 H.sub.5                                                               NH.sub.2  COOCH.sub.3                                           262  SO.sub.2 -nC.sub.3 H.sub.7                                                               NH.sub.2  COOCH.sub.3                                           263  SO.sub.2 -isoC.sub.3 H.sub.7                                                             NH.sub.2  COOCH.sub.3                                           264  SO.sub.2 -nC.sub.4 H.sub.9                                                               NH.sub.2  COOCH.sub.3                                           265  SO.sub.2 -isoC.sub.4 H.sub.9                                                             NH.sub.2  COOCH.sub.3                                           266  SO.sub.2 -secC.sub.4 H.sub.9                                                             NH.sub.2  COOCH.sub.3                                           267  SO.sub.2 -tertC.sub.4 H.sub.9                                                            NH.sub.2  COOCH.sub.3                                           268  SO.sub.2 -nC.sub.5 H.sub.11                                                              NH.sub.2  COOCH.sub.3                                           269  SO.sub.2 -neoC.sub.5 H.sub.11                                                            NH.sub.2  COOCH.sub.3                                           270  SO.sub.2 -nC.sub.6 H.sub.13                                                              NH.sub.2  COOCH.sub.3                                           271  SO.sub.2 -nC.sub.7 H.sub.15                                                              NH.sub.2  COOCH.sub.3                                           272  SO.sub.2 -nC.sub.8 H.sub.17                                                              NH.sub.2  COOCH.sub.3                                           273  SO.sub.2 -nC.sub.9 H.sub.19                                                              NH.sub.2  COOCH.sub.3                                           274  SO.sub.2 -nC.sub.10 H.sub.21                                                             NH.sub.2  COOCH.sub.3                                           275  SO.sub.2 -nC.sub.11 H.sub.23                                                             NH.sub.2  COOCH.sub.3                                           276  SO.sub.2 -nC.sub.12 H.sub.25                                                             NH.sub.2  COOCH.sub.3                                           277  SO.sub.2 -nC.sub.13 H.sub.27                                                             NH.sub.2  COOCH.sub.3                                           278  SO.sub.2 -nC.sub.14 H.sub.29                                                             NH.sub.2  COOCH.sub.3                                           279  SO.sub.2 -nC.sub.15 H.sub.31                                                             NH.sub.2  COOCH.sub.3                                           280  SO.sub.2 -nC.sub.16 H.sub.33                                                             NH.sub.2  COOCH.sub.3                                           281  SO.sub.2 -nC.sub.17 H.sub.35                                                             NH.sub.2  COOCH.sub.3                                           282  SO.sub.2 -nC.sub.18 H.sub.37                                                             NH.sub.2  COOCH.sub.3                                           283  SO.sub.2 -nC.sub.19 H.sub.39                                                             NH.sub.2  COOCH.sub.3                                           284  SO.sub.2 -nC.sub.20 H.sub.41                                                             NH.sub.2  COOCH.sub.3                                           285  S-Cyclopropyl                                                                            NH.sub.2  COOCH.sub.3                                           286  S-Cycloprentyl                                                                           NH.sub.2  COOCH.sub.3                                           287  S-Cyclohexyl                                                                             NH.sub.2  COOCH.sub.3                                           288  S-Cycloheptyl                                                                            NH.sub.2  COOCH.sub.3                                           289  S-Cyclooctyl                                                                             NH.sub.2  COOCH.sub.3                                           290  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COOCH.sub.3                                           291  SO.sub.2 --CH.sub.2 C.sub. 6 H.sub.5                                                     NH.sub.2  COOCH.sub.3                                           292  SO.sub.2 --(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                            NH.sub.2  COOCH.sub.3                                           293  SO.sub.2 --CH.sub.2 CH.sub.2 OH                                                          NH.sub.2  COOCH.sub.3                                           294  SO.sub.2 --CH.sub.2 --CH═CH.sub.2                                                    NH.sub.2  COOCH.sub.3                                           295  SO.sub.2 --CH.sub.2 --CH.tbd.CH                                                          NH.sub.2  COOCH.sub.3                                           296  S--CH.sub.2 COOH                                                                         NH.sub.2  CHO                                                   297  S--CH.sub.2 COOCH.sub.3                                                                  NH.sub.2  CHO                                                   298  S--CH.sub.2 COOC.sub.2 H.sub.5                                                           NH.sub.2  CHO                                                   299  S--CH.sub.2 COOH                                                                         NH.sub.2  CN                                                    300  S--CH.sub.2 COOCH.sub.3                                                                  NH.sub.2  CN                                                    301  S--CH.sub.2 COOC.sub.2 H.sub.5                                                           NH.sub.2  CN                                                    302  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CH═C(CN).sub.2                                    303  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CH═C(CN).sub.2                                    304  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CH═C(CN).sub.2                                    305  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CH═C(CN).sub.2                                    306  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CH═C(CN)(COOCH.sub.3)                             307  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CH═C(CN)(COOCH.sub.3)                             308  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CH═C(CN)(COOCH.sub.3)                             309  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CH═C(CN)(COOCH.sub.3)                             310  S-nC.sub.4 H.sub.9                                                                       N═CH--N(CH.sub.3).sub.2                                                              CHO                                                   311  S--C.sub.6 H.sub.5                                                                       N═CH--N(CH.sub.3).sub.2                                                              CHO                                                   312  S--CH.sub.2 C.sub.6 H.sub.5                                                              N═CH--N(CH.sub.3).sub.2                                                              CHO                                                   313  S--C.sub.2 H.sub.5                                                                       N═CH--N(CH.sub.3).sub.2                                                              CHO                                                   314  SH        N═CH--N(CH.sub.3).sub.2                                                              CHO                                                   315  SO.sub.2 --C.sub.6 H.sub.5                                                               N═CH--N(CH.sub.3).sub.2                                                              CHO                                                   316  S-nC.sub.4 H.sub.9                                                                       N═CH--N(CH.sub.3).sub.2                                                              CN                                                    317  S--C.sub.6 H.sub.5                                                                       N═CH--N(CH.sub.3).sub.2                                                              CN                                                    318  S--CH.sub.2 C.sub.6 H.sub.5                                                              N═CH--N(CH.sub.3).sub.2                                                              CN                                                    319  S--C.sub.2 H.sub.5                                                                       N═CH--N(CH.sub.3).sub.2                                                              CN                                                    320  SH        N═CH--N(CH.sub.3).sub.2                                                              CN                                                    321  SO.sub.2 --C.sub.6 H.sub.5                                                               N═CH--N(CH.sub.3).sub.2                                                              CN                                                    322  SO.sub.2 --(CH.sub.2).sub.3 C.sub.6 H.sub.5                                              NH.sub.2  CHO                                                   323  S--(CH.sub.2).sub.3 C.sub.6 H.sub.5                                                      NH.sub. 2 CHO                                                   324  S--CH(CH.sub.3)C.sub.6 H.sub.5                                                           NH.sub.2  CHO                                                   325  S--CH(C.sub.2 H.sub.5)C.sub.6 H.sub.5                                                    NH.sub.2  CHO                                                   326  S--C(CH.sub.3).sub.2 C.sub.6 H.sub.5                                                     NH.sub.2  CHO                                                   327  SO.sub.2 --(CH.sub.2).sub.3 C.sub.6 H.sub.5                                              NH.sub.2  CN                                                    328  S--(CH.sub.2).sub.3 C.sub.6 H.sub.5                                                      NH.sub.2  CN                                                    329  S--CH(CH.sub.3)C.sub.6 H.sub.5                                                           NH.sub.2  CN                                                    330  S--CH(C.sub.2 H.sub.5)C.sub.6 H.sub.5                                                    NH.sub.2  CN                                                    331  S--C(CH.sub.3).sub.2 C.sub.6 H.sub.5                                                     NH.sub.2  CN                                                    332  S--C.sub.6 H.sub.5                                                                       N═CH-morpholino                                                                      CHO                                                   333  S--CH.sub.2 C.sub.6 H.sub.5                                                              N═CH-pyrollidino                                                                     CHO                                                   334  SO.sub.2 --C.sub.6 H.sub.5                                                               N═CH-piperidino                                                                      CHO                                                   335  S--C.sub.2 H.sub.5                                                                       N═CH-piperazino                                                                      CN                                                    336  S--C.sub.6 H.sub.5                                                                       N═CH-thiomorpholino                                                                  CHO                                                   337  S--CH.sub.2 C.sub.6 H.sub.5                                                              N═CH-hexamethyleneimino                                                              CN                                                    338  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COCH.sub.3                                            339  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COCH.sub.3                                            340  S--nC.sub.4 H.sub.9                                                                      NH.sub.2  COCH.sub.3                                            341  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COCH.sub.3                                            342  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COCH.sub.3                                            343  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CO.sub.2 C.sub.2 H.sub.5                              344  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COC.sub.2 H.sub.5                                     345  S--nC.sub.4 H.sub.9                                                                      NH.sub.2  COC.sub.2 H.sub.5                                     346  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COC.sub.2 H.sub.5                                     347  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COC.sub.2 H.sub.5                                     348  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CO-nC.sub.3 H.sub.7                                   349  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CO-nC.sub.4 H.sub.9                                   350  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CO-nC.sub.5 H.sub.11                                  351  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CO-nC.sub.6 6.sub.13                                  352  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CO-nC.sub.6 H.sub.13                                  353  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COC.sub.6 H.sub.5                                     354  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COC.sub.6 H.sub.5                                     355  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  COC.sub.6 H.sub.5                                     356  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COC.sub.6 H.sub.5                                     357  SO.sub.2 -- C.sub.6 H.sub.5                                                              NH.sub.2  COC.sub.6 H.sub.5                                     358  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COOC.sub.2 H.sub.5                                    359  S--nC.sub.4 H.sub.9                                                                      NH.sub.2  COOC.sub.2 H.sub.5                                    360  S--nC.sub.6 H.sub.13                                                                     NH.sub.2  COOC.sub.2 H.sub.5                                    361  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COOC.sub.2 H.sub.5                                    362  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COOC.sub.2 H.sub.5                                    363  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COOC.sub.2 H.sub.5                                    364  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COO-nC.sub.3 H.sub.7                                  365  S--nC.sub.4 H.sub.9                                                                      NH.sub.2  COO-nC.sub.3 H.sub.7                                  366  S--nC.sub.6 H.sub.13                                                                     NH.sub.2  COO-nC.sub.3 H.sub.7                                  367  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COO-nC.sub.3 H.sub.7                                  368  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COO-nC.sub.3 H.sub.7                                  369  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COO-nC.sub.3 H.sub.7                                  370  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COO-nC.sub.4 H.sub.9                                  371  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  COO-nC.sub.4 H.sub.9                                  372  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  COO-nC.sub.4 H.sub.9                                  373  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COO-nC.sub.4 H.sub.9                                  374  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COO-nC.sub.4 H.sub.9                                  375  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COO-nC.sub.4 H.sub.9                                  376  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COO-nC.sub.5 H.sub.11                                 377  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  COO-nC.sub.5 H.sub.11                                 378  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  COO-nC.sub.5 H.sub.11                                 379  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COO-nC.sub.5 H.sub.11                                 380  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COO-nC.sub.5 H.sub.11                                 381  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COO-nC.sub.5 H.sub.11                                 382  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COO-nC.sub.6 H.sub.13                                 383  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  COO-nC.sub.6 H.sub.13                                 384  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  COO-nC.sub.6 H.sub.13                                 385  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COO-nC.sub.6 H.sub.13                                 386  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COO-nC.sub.6 H.sub.13                                 387  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COO-nC.sub.6 H.sub.13                                 388  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COOC.sub.6 H.sub.5                                    389  S-nC.sub.4 H.sub. 9                                                                      NH.sub.2  COOC.sub.6 H.sub.5                                    390  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  COOC.sub.6 H.sub.5                                    391  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COOC.sub.6 H.sub.5                                    392  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COOC.sub.6 H.sub.5                                    393  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COOC.sub.6 H.sub.5                                    394  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CONH.sub.2                                            395  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CONH.sub.2                                            396  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CONH.sub.2                                            397  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CONH.sub.2                                            398  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CONH.sub.2                                            399  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CONH.sub.2                                            400  S--C.sub.6 H.sub.5                                                                       NH.sub.2  C(CH.sub.3)═C(CN).sub.2                           401  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  C(C.sub.6 H.sub.5)═C(CN).sub.2                    402  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CON(CH.sub.3).sub.2                                   403  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CON(CH.sub.3).sub.2                                   404  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CON(CH.sub.3).sub.2                                   405  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CON(CH.sub.3).sub.2                                   406  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CON(CH.sub.3).sub.2                                   407  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CON(CH.sub.3).sub.2                                   408  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CON(C.sub.2 H.sub.5).sub.2                            409  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CON(C.sub.2 H.sub.5).sub.2                            410  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CON(C.sub.2 H.sub.5).sub.2                            411  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CON(C.sub.2 H.sub.5).sub.2                            412  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CON(C.sub.2 H.sub.5).sub.2                            413  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CON(C.sub.2 H.sub.5).sub.2                            414  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CON(C.sub.3 H.sub.7).sub.2                            415  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CON(C.sub.3 H.sub.7).sub.2                            416  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CON(C.sub.3 H.sub.7).sub.2                            417  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CON(C.sub.3 H.sub.7).sub.2                            418  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CON(C.sub.3 H.sub.7).sub.2                            419  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CON(C.sub.3 H.sub.7).sub.2                            420  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CON(C.sub.4 H.sub.9).sub.2                            421  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CON(C.sub.5 H.sub.11).sub.2                           422  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CON(C.sub.6 H.sub.11).sub.2                           423  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CON(CH.sub.3)(C.sub.6 H.sub.5)                        424  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CON(C.sub.2 H.sub.5)(C.sub.6 H.sub.5)                 425  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CON(CH.sub.3)(C.sub.2 H.sub.5)                        426  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CON(n-C.sub.3 H.sub.7)(C.sub.6 H.sub.5)               427  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CON(n-C.sub.4 H.sub.9)(C.sub.6 H.sub.5)               428  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CON(n-C.sub.6 H.sub.13)(C.sub.6 H.sub.5)              429  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CH═C(CN)(NO.sub.2)                                430  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CH═C(CN)(NO.sub.2)                                431  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CH═C(CN)(CONH.sub.2)                              432  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CH═C(CN)(CONH.sub.2)                              433  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CH═C(CN)(CONH.sub. 2)                             434  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CH═C(CN)(CONH.sub.2)                              435  S--C.sub.2 H.sub.5                                                                       NH.sub.2  C(CH.sub.3)═C(CN).sub.2                           436  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  C(CH.sub.3)═C(CN)(NO.sub.2)                       437  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  C(C.sub.6 H.sub.5)═C(CN).sub.2                    438  S--C.sub.6 H.sub.5                                                                       NH.sub.2  C(C.sub.6 H.sub.5)═C(CN).sub.2                    439  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  C(C.sub.6 H.sub.5)═C(CN).sub.2                    440  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  C(C.sub.6 H.sub.5)═C(CN).sub.2                    441  S--C.sub.6 H.sub.4 -p-CH.sub.3                                                           NH.sub.2  CHO           204.5-205                               442  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CO-Morpholino                                         443  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CO-Morpholino                                         444  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CO-Morpholino                                         445  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CO-Morpholino                                         446  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CO-Morpholino                                         447  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CO-Morpholino                                         448  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CO-Piperidino                                         449  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CO-Piperidino                                         450  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CO-Piperidino                                         451  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CO-Piperidino                                         452  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CO-Piperidino                                         453  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CO-Piperidino                                         454  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CO-Pyrrolidino                                        455  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CO-Pyrrolidino                                        456  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CO-Pyrrolidino                                        457  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CO-Pyrrolidino                                        458  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CO-Pyrrolidino                                        459  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CO-Pyrrolidino                                        460  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CO-Thiomorpholino                                     461  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CO-Thiomorpholino                                     462  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CO-Thiomorpholino                                     463  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CO-hexamethyleneimino                                 464  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CO-hexamethyleneimino                                 465  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CO-hexamethyleneimino                                 466  S--C.sub.2 H.sub.5                                                                       NH.sub.2  CO--(N-Methyl-piperazino)                             467  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  CO--(N-Methyl-piperazino)                             468  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  CO--(N-Ethyl-piperazino)                              469  S--C.sub.6 H.sub.5                                                                       NH.sub.2  CO--(N-Ethyl-piperazino)                              470  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  CO--(N-Ethyl-piperazino)                              471  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  CO--(N-Ethyl-piperazino)                              472  S--C.sub.2 H.sub.5                                                                       NH.sub.2  COO-Cyclopropyl                                       473  S-nC.sub.4 H.sub.9                                                                       NH.sub.2  COO-Cyclopropyl                                       474  S-nC.sub.6 H.sub.13                                                                      NH.sub.2  COO-Cyclopentyl                                       475  S--C.sub.6 H.sub.5                                                                       NH.sub.2  COO-Cyclopentyl                                       476  S--CH.sub.2 C.sub.6 H.sub.5                                                              NH.sub.2  COO-Cyclohexyl                                        477  SO.sub.2 --C.sub.6 H.sub.5                                                               NH.sub.2  COO-Cyclohexyl                                        __________________________________________________________________________

EXAMPLE 478

8.1 g of 2-amino-4-chloro-5-formylthiazole were dissolved in 40 ml of N,N-dimethylformamide and, at 35° to 40° C., 9.9 ml of piperidine were added dropwise. The reaction mixture was then stirred at room temperature for 4 hours and subsequently poured into 150 ml of ice-water. The precipitate was filtered off with suction, washed with water and dried at 50° C. under reduced pressure. 6.3 g (60% of theory) of the compound of the formula ##STR28## were obtained of melting point 160° C. (decomposition). The NMR, IR, UV and mass spectra and the elemental analysis are consistent with the indicated structure.

EXAMPLE 479

8 g of 2-amino-4-chloro-5-cyanothiazole were dissolved in 50 ml of N,N-dimethylformamide and, at 35° C., 7.9 ml of 70% by weight aqueous ethylamine solution were added dropwise. The reaction mixture was stirred at room temperature for 1 hour and then a further 1 ml of 70% by weight aqueous ethylamine solution was added. The reaction mixture was stirred at room temperature for a further 0.5 hour and then poured into 400 ml of ice-water and 5 ml of hydrochloric acid (M 100). The precipitate was filtered off with suction, washed with water and dried at 50° C. under reduced pressure. 4.0 g (48% of theory of the compound of the formula ##STR29## were obtained of melting point 171°-174° C. The NMR, IR, UV and mass spectra and the elemental analysis are consistent with the structure indicated above.

The compounds of the formula ##STR30## which are listed in Table 2 which follows can be prepared in a similar manner.

                                      TABLE 2                                      __________________________________________________________________________                                             Melting                                Example                                 point                                  no.  R.sup.3           NR.sup.1 R.sup.2                                                                         R.sup.4                                                                               (°C.)                           __________________________________________________________________________     480  NH--CH.sub.3      NH.sub.2  CN                                            481  NH-nC.sub.3 H.sub.7                                                                              NH.sub.2  CN     121-23                                 482  NH-isoC.sub.3 H.sub.7                                                                            NH.sub.2  CN     134-36                                 483  NH-nC.sub.4 H.sub.9                                                                              NH.sub.2  CN                                            484  NH-secC.sub.4 H.sub.9                                                                            NH.sub.2  CN                                            485  NH-isoC.sub.4 H.sub.9                                                                            NH.sub.2  CN     203-05                                 486  NH-tertC.sub.4 H.sub.9                                                                           NH.sub.2  CN     152-53                                 487  NH-nC.sub.5 H.sub.11                                                                             NH.sub.2  CN                                            488  NH-isoC.sub.5 H.sub.11                                                                           NH.sub.2  CN                                            489  NH--CH(CH.sub.3)--CH(CH.sub.3).sub.2                                                             NH.sub.2  CN                                            490  NH-neoC.sub.5 H.sub.11                                                                           NH.sub.2  CN     117-19                                 491  NH-nC.sub.6 H.sub.13                                                                             NH.sub.2  CN                                            492  NH-nC.sub.7 H.sub.15                                                                             NH.sub.2  CN                                            493  NH-nC.sub.8 H.sub.17                                                                             NH.sub.2  CN                                            494  NH-nC.sub.9 H.sub.19                                                                             NH.sub.2  CN                                            495  NH-nC.sub.10 H.sub.21                                                                            NH.sub.2  CN                                            496  NH-nC.sub.12 H.sub.25                                                                            NH.sub.2  CN                                            497  NH-nC.sub.13 H.sub.27                                                                            NH.sub.2  CN                                            498  NH-nC.sub.16 H.sub.33                                                                            NH.sub.2  CN                                            499  NH-nC.sub.18 H.sub.37                                                                            NH.sub.2  CN                                            500  NH--CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3                                                       NH.sub.2  CN                                            501  NH--CH(CH.sub.3)--(CH.sub.2).sub.3 CH.sub.3                                                      NH.sub.2  CN                                            502  NH--CH(CH.sub.3)--(CH.sub.2).sub.2 --CH(CH.sub.3).sub.2                                          NH.sub.2  CN                                            503  NH--CH(CH.sub.3)--(CH.sub.2).sub.5 --CH.sub.3                                                    NH.sub.2  CN                                            504  NH--CH(C.sub.2 H.sub.5)--(CH.sub.2).sub.4 --CH.sub.3                                             NH.sub.2  CN                                            505  NH--CH(CH.sub.3)--(CH.sub.2).sub.3 --CH(CH.sub.3).sub.2                                          NH.sub.2  CN                                            506  (R)--(-)--NH--CH(CH.sub.3)-Cyclohexyl                                                            NH.sub.2  CN                                            507  (S)--(+)--NH--CH(CH.sub.3)-Cyclohexyl                                                            NH.sub.2  CN                                            508  NH--CH.sub.2 CH.sub.2 -Cyclohexyl                                                                NH.sub.2  CN                                            509  NH--(CH.sub.2).sub.2 --OH                                                                        NH.sub.2  CN                                            510  NH--(CH.sub.2).sub.2 --OCH.sub.3                                                                 NH.sub.2  CN                                            511  NH--(CH.sub.2).sub.2 --OC.sub.2 H.sub.5                                                          NH.sub.2  CN                                            512  NH--(CH.sub.2).sub.2 --OC.sub.6 H.sub.5                                                          NH.sub.2  CN                                            513  NH--(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 OH                                                    NH.sub.2  CN                                            514  NH--(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.2 OH                                                   NH.sub.2  CN                                            515  NH--(CH.sub.2).sub.2 --NH.sub.2                                                                  NH.sub.2  CN                                            516  NH--(CH.sub.2).sub.2 --N(CH.sub.3).sub.2                                                         NH.sub.2  CN                                            517  NH--(CH.sub.2).sub.2 --N(C.sub.2 H.sub.5).sub.2                                                  NH.sub.2  CN                                            518  NH--(CH.sub.2).sub.2 --N(iso-C.sub.3 H.sub.7).sub.2                                              NH.sub.2  CN                                            519  NH--(CH.sub.2).sub.2 -Piperazino                                                                 NH.sub.2  CN                                            520  NH--(CH.sub.2).sub.3 OH                                                                          NH.sub.2  CN                                            521  NH--(CH.sub.2).sub.3 OCH.sub.3                                                                   NH.sub.2  CN                                            522  NH--(CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                            NH.sub.2  CN                                            523  NH--(CH.sub.2).sub.3 --OCH(CH.sub.3).sub.2                                                       NH.sub.2  CN                                            524  NH--(CH.sub.2).sub.3 --OC.sub.6 H.sub.5                                                          NH.sub.2  CN                                            525  NH--(CH.sub.2).sub.3 --O--CH.sub.2 C.sub.6 H.sub.5                                               NH.sub.2  CN                                            526  NH--(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--CH.sub.3                                         NH.sub.2  CN                                            527  NH--(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --O--C.sub.2 H.sub.                                   NH.sub.2  CN                                            528  NH--(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                  NH.sub.2  CN                                            529  NH--(CH.sub.2).sub.3 --NH.sub.2                                                                  NH.sub.2  CN                                            530  NH--(CH.sub.2).sub.3 --N(CH.sub.3).sub.2                                                         NH.sub.2  CN                                            531  NH--(CH.sub.2).sub.3 --N(C.sub.2 H.sub.5).sub.2                                                  NH.sub.2  CN                                            532  NH--(CH.sub.2).sub.3 --N(n-C.sub.4 H.sub.9).sub.2                                                NH.sub.2  CN                                            533  NH--(CH.sub.2).sub.3-Morpholino                                                                  NH.sub.2  CN                                            534  NH--(CH.sub.2).sub.4--OH                                                                         NH.sub.2  CN                                            535  NH--(CH.sub.2).sub.5--NH.sub.2                                                                   NH.sub.2  CN                                            536  NH--(CH.sub.2).sub.6--OH                                                                         NH.sub.2  CN                                            537  NH--(CH.sub.2).sub.6--NH.sub.2                                                                   NH.sub.2  CN                                            538  NH--(CH.sub.2).sub.7--NH.sub.2                                                                   NH.sub.2  CN                                            539  NH--(CH.sub.2).sub.8--NH.sub.2                                                                   NH.sub.2  CN                                            540  NH--(CH.sub.2).sub.9--NH.sub.2                                                                   NH.sub.2  CN                                            541  NH--(CH.sub.2).sub.10--NH.sub.2                                                                  NH.sub.2  CN                                            542  NH--(CH.sub.2).sub.12--NH.sub.2                                                                  NH.sub.2  CN                                            543  NH--CH(CH.sub.3)--(CH.sub.2).sub.3 --N(C.sub. 2 H.sub.5).sub.2                 × HCl       NH.sub.2  CN                                            544  NH--(CH.sub.2)--CH(CH.sub.3)--OH                                                                 NH.sub.2  CN                                            545  NH--CH(CH.sub.3)--CH.sub.2 --OH                                                                  NH.sub.2  CN                                            546  NH--CH.sub.2 -2-Thienyl                                                                          NH.sub.2  CN                                            547  NH--C(CH.sub.3).sub.2 --CH.sub.2 --OH                                                            NH.sub.2  CN                                            548  NH--C(CH.sub.3)--(CH.sub.2 --OH).sub.2                                                           NH.sub.2  CN                                            549  NH--CH(C.sub.2 H.sub.5)--CH.sub.2 --OH                                                           NH.sub.2  CN                                            550  NH--(CH.sub.2).sub.2 --COOH                                                                      NH.sub.2  CN                                            551  NH--(CH.sub.2).sub.5 --COOH                                                                      NH.sub.2  CN                                            552  NH--(CH.sub.2).sub.10 --COOH                                                                     NH.sub.2  CN                                            553  NH--C.sub.6 H.sub.5                                                                              NH.sub.2  CN                                            554  NH--C.sub.6 H.sub.4 -(2)-CH.sub.3                                                                NH.sub.2  CN                                            555  NH--C.sub.6 H.sub.4 -(3)-CH.sub.3                                                                NH.sub.2  CN                                            556  NH--C.sub.6 H.sub.4 -(4)-CH.sub.3                                                                NH.sub.2  CN                                            557  NH--C.sub.6 H.sub.5 -(2)-C.sub.2 H.sub.5                                                         NH.sub.2  CN                                            558  NH--C.sub.6 H.sub.4 -(4)-C.sub.2 H.sub.5                                                         NH.sub.2  CN                                            559  NH--C.sub.6 H.sub.4 -(2)-CF.sub.3                                                                NH.sub.2  CN                                            560  NH--C.sub. 6 H.sub.4 -(3)-CF.sub.3                                                               NH.sub.2  CN                                            561  NH--C.sub.6 H.sub.4 -(4)-CF.sub.3                                                                NH.sub.2  CN                                            562  NH--C.sub.6 H.sub.5 -(2)-OH                                                                      NH.sub.2  CN                                            563  NH--C.sub.6 H.sub.5 -(3)-OH                                                                      NH.sub.2  CN                                            564  NH--C.sub.6 H.sub.5 -(4)-OH                                                                      NH.sub.2  CN                                            565  NH--C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                               NH.sub.2  CN                                            566  NH--C.sub.6 H.sub.4 -(3)-OCH.sub.3                                                               NH.sub.2  CN                                            567  NH--C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                               NH.sub.2  CN                                            568  NH--C.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                        NH.sub.2  CN                                            569  NH--C.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                        NH.sub.2  CN                                            570  NH--C.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                        NH.sub.2  CN                                            571  NH--C.sub.6 H.sub.4 -(2)-Cl                                                                      NH.sub.2  CN                                            572  NH--C.sub.6 H.sub.4 -(3)-Cl                                                                      NH.sub.2  CN                                            573  NH--C.sub.6 H.sub.4 -(4)-Cl                                                                      NH.sub.2  CN                                            574  NH--C.sub.6 H.sub.4 -(2)-F                                                                       NH.sub.2  CN                                            575  NH--C.sub.6 H.sub.4 -(3)-F                                                                       NH.sub.2  CN                                            576  NH--C.sub.6 H.sub.4 -(4)-F                                                                       NH.sub.2  CN                                            577  NH--C.sub.6 H.sub.4 -(2)-Br                                                                      NH.sub.2  CN                                            578  NH--C.sub.6 H.sub.4 -(3)-Br                                                                      NH.sub.2  CN                                            579  NH--C.sub.6 H.sub.4 -(4)-Br                                                                      NH.sub.2  CN                                            580  NH--C.sub.6 H.sub.4 -(2)-I                                                                       NH.sub.2  CN                                            581  NH--C.sub.6 H.sub.4 -(3)-I                                                                       NH.sub.2  CN                                            582  NH--C.sub.6 H.sub.4 -(4)-I                                                                       NH.sub.2  CN                                            583  NH--C.sub.6 H.sub.4 -(2)-NH.sub.2                                                                NH.sub.2  CN                                            584  NH--C.sub.6 H.sub.4 -(3)-NH.sub.2                                                                NH.sub.2  CN                                            585  NH--C.sub.6 H.sub.4 -(4)-NH.sub.2                                                                NH.sub.2  CN                                            586  NH--C.sub.6 H.sub.4 -(4)-NH--COCH.sub.3                                                          NH.sub.2  CN                                            587  NH--C.sub.6 H.sub.4 -(2)-CH.sub.2 OH                                                             NH.sub.2  CN                                            588  NH--C.sub.6 H.sub.4 -(3)-CH.sub.2 OH                                                             NH.sub.2  CN                                            589  NH--C.sub.6 H.sub.4 -(4)-COCH.sub.3                                                              NH.sub.2  CN                                            590  NH--C.sub.6 H.sub.4 -(2)-COOH                                                                    NH.sub.2  CN                                            591  NH--C.sub.6 H.sub.4 -(3)-COOH                                                                    NH.sub.2  CN                                            592  NH--C.sub.6 H.sub.4 -(4)-COOH                                                                    NH.sub.2  CN                                            593  NH--C.sub.6 H.sub.4 -(2)-CONH.sub.2                                                              NH.sub.2  CN                                            594  NH--C.sub.6 H.sub.4 -(4)-CONH.sub.2                                                              NH.sub.2  CN                                            595  NH--C.sub.6 H.sub.4 -(2)-CN                                                                      NH.sub.2  CN                                            596  NH--C.sub.6 H.sub.4 -(3)-CN                                                                      NH.sub.2  CN                                            597  NH--C.sub.6 H.sub.4 -(4)-CN                                                                      NH.sub.2  CN                                            598  NH--C.sub.6 H.sub.3 -(2,6)-(CH.sub.3).sub.2                                                      NH.sub.2  CN                                            599  NH--C.sub.6 H.sub.3 -(3,5)-(CH.sub.3).sub.2                                                      NH.sub.2  CN                                            600  NH--C.sub.6 H.sub.3 -(2)-OH-(5)-CH.sub.3                                                         NH.sub.2  CN                                            601  NH--C.sub.6 H.sub.3 -(2)-OH-(4)-CH.sub.3                                                         NH.sub.2  CN                                            602  NH--C.sub.6 H.sub.3 -(2)-OH-(2)-CH.sub.3                                                         NH.sub.2  CN                                            603  NH--C.sub.6 H.sub.3 -(2)-OH-(5)-Cl                                                               NH.sub.2  CN                                            604  NH-2-Pyridyl      NH.sub.2  CN                                            605  NH-3-Pyridyl      NH.sub.2  CN                                            606  NH-4-Pyridyl      NH.sub.2  CN                                            607  NH--CH.sub.2 -3-Pyridyl                                                                          NH.sub.2  CN                                                 NH--CH.sub.2 -2-Furyl                                                                            NH.sub.2  CN                                            608  NH--CH.sub.2 --C.sub.6 H.sub.5                                                                   NH.sub.2  CN     119-22                                 609  NH--CH.sub.2 --C.sub.6 H.sub.4 -(2)-OCH.sub.3                                                    NH.sub.2  CN                                            610  NH--CH.sub.2 --C.sub.6 H.sub.4 -(4)-OCH.sub.3                                                    NH.sub.2  CN                                            611  NH--CH.sub.2 --C.sub.6 H.sub.4 -(4)-F                                                            NH.sub.2  CN                                            612  NH--CH.sub.2 --C.sub.6 H.sub.4 -(2)-Cl                                                           NH.sub.2  CN                                            613  NH--CH.sub.2 --C.sub.6 H.sub.4 -(4)-Cl                                                           NH.sub.2  CN                                            614  NH--CH.sub.2 --C.sub.6 H.sub.3 -(3,4)-(OCH.sub.3).sub.2                                          NH.sub.2  CN                                            615  NH--CH.sub. 2 --CH.sub.2 --C.sub.6 H.sub.5                                                       NH.sub.2  CN                                            616  NH--CH(CH.sub.3)--C.sub.6 H.sub.5 (+/-)                                                          NH.sub.2  CN                                            617  NH--(CH.sub.2).sub.3 --C.sub.6 H.sub.5                                                           NH.sub.2  CN                                            618  NH--CH(CH.sub.3)--(CH.sub.2).sub.2 --C.sub.6 H.sub.5                                             NH.sub.2  CN                                            619  NH-Cyclopropyl    NH.sub.2  CN                                            620  NH-Cyclopentyl    NH.sub.2  CN                                            621  NH-Cyclohexyl     NH.sub.2  CN                                            622  NH-Cycloheptyl    NH.sub.2  CN                                            623  NH-Cyclooctyl     NH.sub.2  CN                                            624  NH-Cyclododecyl   NH.sub.2  CN                                            625  NH--CH.sub.2 --CH═CH.sub.2                                                                   NH.sub.2  CN                                            626  NH--CH.sub.2 --C.tbd.CH                                                                          NH.sub.2  CN                                            627  N(CH.sub.3).sub.2 NH.sub.2  CN                                            628  N(C.sub.2 H.sub.5).sub.2                                                                         NH.sub.2  CN                                            629  N(n-C.sub.3 H.sub.7).sub.2                                                                       NH.sub.2  CN                                            630  N(n-C.sub.4 H.sub.9).sub.2                                                                       NH.sub.2  CN                                            631  N(iso-C.sub.4 H.sub.9).sub.2                                                                     NH.sub.2  CN                                            632  N(n-C.sub.5 H.sub.11).sub.2                                                                      NH.sub.2  CN                                            633  N(sec-C.sub.4 H.sub.9).sub.2                                                                     NH.sub.2  CN                                            634  N(iso-C.sub.5 H.sub.11).sub.2                                                                    NH.sub.2  CN                                            635  N(n-C.sub.6 H.sub.13).sub.2                                                                      NH.sub.2  CN                                            636  N(CH(C.sub.2 H.sub.5)--(CH.sub.2).sub.4 --CH.sub.3).sub.2                                        NH.sub.2  CN                                            637  N(n-C.sub.8 H.sub.17).sub.2                                                                      NH.sub.2  CN                                            638  N(CH.sub.2 --CH═CH.sub.2).sub.2                                                              NH.sub.2  CN                                            639  N(Cyclohexyl).sub.2                                                                              NH.sub.2  CN                                            640  N(CH.sub.3)-nC.sub.4 H.sub.9                                                                     NH.sub.2  CN                                            641  N(CH.sub.3)-Cyclohexyl                                                                           NH.sub.2  CN                                            642  N(C.sub.2 H.sub.5)-Cyclohexyl                                                                    NH.sub.2  CN                                            643  N(CH.sub.3)--(CH.sub.2).sub.2 --OH                                                               NH.sub.2  CN                                            644  N(C.sub.2 H.sub.5)--CH(CH.sub.3)--CH(CH.sub.3).sub.2                                             NH.sub.2  CN                                            645  N(C.sub.2 H.sub.5)--(CH).sub.2 --OH                                                              NH.sub.2  CN                                            646  N(C.sub.2 H.sub.5)--CH.sub.2 --CH(OH)--CH.sub.3                                                  NH.sub.2  CN                                            647  N(tert-C.sub.4 H.sub.9)--(CH.sub.2).sub.2 --OH                                                   NH.sub.2  CN                                            648  N(CH.sub.3)--C.sub.6 H.sub.5                                                                     NH.sub.2  CN                                            649  N(C.sub.2 H.sub.5)--C.sub.6 H.sub.5                                                              NH.sub.2  CN                                            650  N(iso-C.sub.3 H.sub.7)--C.sub.6 H.sub.5                                                          NH.sub.2  CN                                            651  N(nC.sub.4 H.sub.9)--C.sub.6 H.sub.5                                                             NH.sub.2  CN                                            652  N(CH.sub.2 C.sub.6 H.sub.5).sub.2                                                                NH.sub.2  CN                                            653  N(CH.sub.3)--CH.sub.2 C.sub.6 H.sub.5                                                            NH.sub.2  CN                                            654  N(C.sub.2 H.sub.5)--CH.sub.2 C.sub.6 H.sub.5                                                     NH.sub.2  CN                                            655  N(iso-C.sub.3 H.sub.7)--CH.sub.2 C.sub.6 H.sub.5                                                 NH.sub.2  CN                                            656  N(tert-C.sub.4 H.sub.9)--CH.sub.2 C.sub.6 H.sub.5                                                NH.sub.2  CN                                            657  N(CH.sub.2 C.sub.6 H.sub.5)--(CH.sub.2).sub.2 --)OH                                              NH.sub.2  CN                                            658  N(C.sub.6 H.sub.5)--CH.sub.2 C.sub.6 H.sub.5                                                     NH.sub.2  CN                                            659  N(CH.sub.2 C.sub.6 H.sub.5)--((CH.sub.2).sub.2 --C.sub.6 H.sub.5)                                NH.sub.2  CN                                            660  Pyrrolidino       NH.sub.2  CN                                            661  Hexamethyleneimino                                                                               NH.sub.2  CN                                            662  N-Methylpiperazino                                                                               NH.sub.2  CN                                            663  NH--NH.sub.2      NH.sub.2  CN                                            664  NH--NH--CH.sub.3  NH.sub.2  CN                                            665  NH--NH--C.sub.6 H.sub.5                                                                          NH.sub.2  CN                                            666  NH--N(CH.sub.3).sub.2                                                                            NH.sub.2  CN                                            667  NH--OH            NH.sub.2  CN                                            668  NH--CH.sub.3      NH.sub.2  CHO                                           669  NH--C.sub.2 H.sub.5                                                                              NH.sub.2  CHO                                           670  NH-nC.sub.3 H.sub.7                                                                              NH.sub.2  CHO                                           671  NH-isoC.sub.3 H.sub.7                                                                            NH.sub.2  CHO                                           672  NH-secC.sub.4 H.sub.9                                                                            NH.sub.2  CHO                                           673  NH-nC.sub.5 H.sub.11                                                                             NH.sub.2  CHO                                           674  NH-Cyclohexyl     NH.sub.2  CHO                                           675  NH--C.sub.6 H.sub.5                                                                              NH.sub.2  CHO                                           676  N(C.sub.2 H.sub.5).sub.2                                                                         NH.sub.2  CHO                                           677  NH--CH.sub.3      N═CH--N(CH.sub.3).sub.2                                                              CN                                            678  NH--C.sub.2 H.sub.5                                                                              N═CH--N(CH.sub.3).sub.2                                                              CN                                            679  NH--CH.sub.3      NH.sub.2  CH═C(CN).sub.2                            680  NH--C.sub.2 H.sub.5                                                                              NH.sub.2  CH═C(CN).sub.2                            681  NH-nC.sub.3 H.sub.7                                                                              NH.sub.2  CH═C(CN).sub.2                            682  NH-nC.sub.4 H.sub.9                                                                              NH.sub.2  CH═C(CN).sub.2                            683  NH-secC.sub.4 H.sub.9                                                                            NH.sub.2  CH═C(CN).sub.2                            684  NH-nC.sub.6 H.sub.13                                                                             NH.sub.2  CH═C(CN).sub.2                            685  NH-nC.sub.7 H.sub.15                                                                             NH.sub.2  CH═C(CN).sub.2                            686  NH--C.sub.2 H.sub.4 --OH                                                                         NH.sub.2  CH═C(CN).sub.2                            687  NH--C.sub.2 H.sub.4 --OCH.sub.3                                                                  NH.sub.2  CH═C(CN).sub.2                            688  NH-Cyclohexyl     NH.sub.2  CH═C(CN).sub.2                            689  NH--C.sub.6 H.sub.5                                                                              NH.sub.2  CH═C(CN).sub.2                            690  NH--C.sub.6 H.sub.4 -(3)-CH.sub.3                                                                NH.sub.2  CH═C(CN).sub.2                            691  NH--CH.sub.2 --C.tbd.CH                                                                          NH.sub.2  CH═C(CN).sub.2                            692  NH(CH.sub.3).sub.2                                                                               NH.sub.2  CH═C(CN).sub.2                            693  Pyrrolidino       NH.sub.2  CH═C(CN).sub.2                            694  Piperidino        NH.sub.2  CH═C(CN).sub.2                            695  Morpholino        NH.sub.2  CH═C(CN).sub.2                            696  NH--NH.sub.2      NH.sub.2  CH═C(CN).sub.2                            697  NH-nC.sub.3 H.sub.7                                                                              NH.sub.2  CH═C(CN)                                                                          (COOCH.sub.3)                          698  NH-nC.sub.4 H.sub.9                                                                              NH.sub.2  CH═C(CN)                                                                          (COOCH.sub.3)                          699  NH-secC.sub.4 H.sub.9                                                                            NH.sub.2  CH═C(CN)                                                                          (COOCH.sub.3)                          700  NH-nC.sub.5 H.sub.11                                                                             NH.sub.2  CH═C(CN)                                                                          (COOC.sub.2 H.sub.5)                   701  N(C.sub.2 H.sub.5).sub.2                                                                         NH.sub.2  CH═C(CN)                                                                          (COOC.sub.2 H.sub.5)                   702  NH--CH.sub.3      NH.sub.2  CH═C(CN)                                                                          (NO.sub.2)                             703  NH-isoC.sub.3 H.sub.7                                                                            NH.sub.2  CH═C(CN)                                                                          (NO.sub.2)                             704  (R/S)--NH--CH(CH.sub.3)-Cyclohexyl                                                               NH.sub.2  CN                                            705  NH--(CH.sub.2).sub.3 --N(n-C.sub.3 H.sub.7).sub.2                                                NH.sub.2  CN                                            706  NH--(CH.sub.2).sub.3 --N(iso-C.sub.3 H.sub.7).sub.2                                              NH.sub.2  CN                                            707  NH--(+)--CH(CH.sub.3)--C.sub.6 H.sub.5                                                           NH.sub.2  CN                                            708  NH--(-)--CH(CH.sub.3)--C.sub.6 H.sub.5                                                           NH.sub.2  CN                                            709  NH-Cyclobutyl     NH.sub.2  CN                                            710  NH-Adamantyl      NH.sub.2  CN                                            711  NH-Cyclononyl     NH.sub.2  CN                                            712  NH-Cyclodecyl     NH.sub.2  CN                                            713  NH-Methallyl      NH.sub.2  CN                                            714  N(isoC.sub.3 H.sub.7).sub.2                                                                      NH.sub.2  CN                                            715  N-Ethylpiperazino NH.sub.2  CN                                            716  Thiomorpholino    NH.sub.2  CN                                            717  NH--NH--C.sub.2 H.sub.5                                                                          NH.sub.2  CN                                            718  NH--N(C.sub.2 H.sub.5).sub.2                                                                     NH.sub.2  CN                                            719  N(CH.sub.3)--NH--CH.sub.3                                                                        NH.sub.2  CN                                            720  1-Imidazolyl      NH.sub.2  CN                                            721  1-Pyrazolyl       NH.sub.2  CN                                            722  NH--CH(CH.sub.3)--(CH.sub.2).sub.4 CH.sub.3                                                      NH.sub.2  CN                                            723  Pyrrolidino       NH.sub.2  CHO    174--176                               __________________________________________________________________________ 

We claim:
 1. An aminothiazole of the formula I ##STR31## or the tautomer thereof, where R¹ and R² are each hydrogen or together form a radical of the formula ##STR32## where T¹ is hydrogen, C₁ -C₆ -alkyl or phenyl and T² and T³ are identical or different and each, independently of one another, is C₁ -C₆ -alkyl, C₅ -C₇ -cycloalkyl or phenyl, or T² and T³ form, together with the nitrogen connecting them, a 5- to 7-membered saturated heterocyclic radical having a single hetero atom or a radical selected from the group consisting of morpholino, thiomorpholino, thiomorpholino S,S-dioxide, piperazino, N-(C₁ -C₄ -alkyl) piperazino and hexamethyleneimino,R³ is

    --S(O).sub.n --X,

where n is 0, 1 or 2 and X is C₁ -C₂₀ -alkyl; C₁ -C₂₀ -alkyl substituted with hydroxyl, C₁ -C₆ -alkoxy, phenyl-C₁ -C₄ -alkoxy, phenoxy, amino, mono- or di-C₁ -C₆ -alkylamino, phenyl-C₁ -C₆ -alkylamino, diphenyl-C₁ -C₄ -alkylamino, phenylamino, diphenylamino, mono- or di-C₃ -C₆ -cycloalkylamino, C₃ -C₆ -cycloalkyl, hydroxy-C₁ -C₆ -alkylamino, morpholino, piperazino, N-(C₁ -C₆ -alkyl)piperazino, thiomorpholino, piperidino, pyrrolidino, hexamethyleneimino, 2-thienyl, 2-furyl, 1H-pyrrol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, phenyl, carboxyl, C₁ -C₃ -alkoxycarbonyl, carbamoyl, mono- or di-C₁ -C₄ -alkylcarbamoyl, cyano, thiocarbamoyl, phenoxycarbamoyl, phenyl-C₁ -C₄ -alkoxycarbonyl, mono- or diphenylcarbamoyl, mono- or di(phenyl-C₁ -C₄ -alkyl)carbamoyl, mono- or diphenylthiocarbamoyl, mono- or di(phenyl-C₁ -C₄ -alkyl)thiocarbamoyl, C₁ -C₆ -alkylthio, phenylthio, phenyl-C₁ -C₄ -alkylthio; C₃ -C₈ -cycloalkyl; C₃ -C₈ -cycloalkyl substituted with florine, chlorine or bromine; C₃ -C₆ -alkenyl; C₃ -C₆ -alkenyl substituted with florine, chlorine or bromine; C₃ -C₆ -alkynyl; C₃ -C₆ -alkynyl substituted with florine, chlorine or bromine; phenyl; phenyl substituted with C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen, nitro, hydroxyl, amino, mono- or di-C₁ -C₆ -alkylamino, acetyl amino, carboxyl, carbamoyl, thiocarbamoyl, cyano, C₁ -C₆ -alkoxy carbonyl, trifluoromethyl, hydroxy-C₁ -C₃ -alkyl, C₁ -C₄ -alkanoyl; or, if n is 0, also hydrogen, or R₃ is Y which means mono- or di-C₁ -C₂₀ -alkylamino, where the alkyl may be substituted as defined above and/or interrupted by one or more oxygen atoms, C₃ -C₈ -cycloalkylamino, adamantylamino, mono- or di-C₂ -C₁₂ -alkenylamino, C₃ -C₁₂ -alkynylamino, N-(C₁ -C₅ -alkyl)-N-phenylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)-piperazino, hexamethyleneimino, 1-imidazolyl, 1-pyrazolyl, phenylamino, phenylamino substituted in the ortho, meta, or para position by methyl, ethyl, trifluoromethyl, hydroxy, methoxy, ethoxy, chloro, fluoro, bromo, iodo, amino, acetyl, hydroxymethyl, carboxyphenyl, aminocabonylphenyl, cyanophenyl; or 2,6-dimethylphenylamino, 3,5-dimethylphenylamino, 2-hydroxy-5-methylphenylamino, 2-hydroxy-4-methylphenylamino, 4-hydroxy-2-methylphenylamino, 2-hydroxy-5-chlorophenylamino; 2-pyridylamino, 3-pyridylamino, 4-pyridylamino, 3-pyridylmethylamino; thienylamino, hydrazino, mono- or di-C₁ -C₄ -alkylhydrazino or phenylhydrazino and R⁴ is C₁ -C₆ -alkanoyl, benzoyl, cyano or ##STR33## where T⁴ is hydroxyl, C₁ -C₆ -alkoxy, amino or the abovementioned radical Y, T⁵ is hydrogen, C₁ -C₆ -alkyl or phenyl and T⁶ is the radical of the active methylene compound ##STR34## where Z is cyano, nitro, C₁ -C₆ -alkanoyl, benzoyl, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, carboxyl, C₁ -C₄ -alkylcarbamoyl, or T⁶ is the radical of ##STR35## hydroxyimino or N-Q where Q is C₁ -C₂₀ -alkyl which may be substituted as described and may be interrupted by one or more oxygen atoms, or C₃ -C₆ -alkenyl, C₃ -C₆ -alkynyl, C₃ -C₁₂ -cycloalkyl or phenyl, each of which may be substituted as described above, pyridyl, C₁ -C₆ -alkoxycarbonylmethyl, amino, di-C₁ -C₄ -alkylamino or phenylamino, with the proviso thata) R³ is not ##STR36## when R¹ and R² are each hydrogen and R⁴ is acetyl or ethoxycarbonyl, b) R³ is not methylthio when R¹ and R² are each hydrogen and R⁴ is cyano, and c) R¹ and R² are not both hydrogen when R³ is piperidino or morpholino and R⁴ is cyano.
 2. An aminothiazole as claimed in claim 1, wherein R¹ and R² are each hydrogen or together form the radical ##STR37## where T¹ is hydrogen, C₁ -C₄ -alkyl or phenyl and T² and T³ are, independently of one another, C₁ -C₄ -alkyl or phenyl, or form, together with the nitrogen atom connecting them, pyrrolidino piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)piperazino or hexamethyleneimino, and R³ and R⁴ each have the meanings specified in claim
 1. 